Titanium and zirconium based metallic glasses and crystalline intermetallic compounds with improved mechanical properties are presently a field of intense application-oriented research. The formation and stability of nanocrystalline phases in Ag-substituted Ti-Zr-Ni alloys was followed using in-situ high-temperature synchrotron radiation diffraction experiments. The substitution of Ti with Ag enhances the formation of amorphous or nanostructured phases during rapid solidification. High-resolution powder diffraction and electron microscopy investigations indicate that the as-quenched alloys are either amorphous or in a mixed nanostructured state. Upon heating, the alloy structure transforms to a fine mixture of icosahedral and crystalline phases depending on the alloy composition and thermal processing parameters. Differential scanning calorimetry studies were performed in order to identify the nature and sequence of the observed structural phase transitions. The experimental results are discussed with respect to the non- equilibrium synthesis and processing of bulk amorphous and bulk nanocrystalline materials in Ti/Zr-based alloys.